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HydroGEN: Photoelectrochemical (PEC) Hydrogen Production
Nemanja Danilovic, Todd Deutsch, Huyen N. Dinh, Adam Z. Weber April 30, 2019 Annual Merit Review
PD148C
Advanced Water-Splitting Materials (AWSM) Relevance, Overall Objective, and Impact
AWSM Consortium 6 Core Labs:
Water
Accelerating R&D of innovative materials critical to advanced water splitting technologies for clean, sustainable & low cost H2 production, including:
Photoelectrochemical (PEC)
Solar Thermochemical (STCH)
Low- and High-Temperature Advanced Electrolysis (LTE & HTE)
H H
Hydrogen
Production target <$2/gge
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HydroGEN: Advanced Water Splitting Materials 3
III-V PEC systems
Particle PEC
systems
Lower III-V costs Optical concentration
Anti-reflection
Higher TRL Lower TRL
Reactor designs Selective catalysis
Gas separation Mass transfer
Absorbers and interfaces processing compatibility
Thin-film PEC
systems
Bandgap tuning Buried junctions Durability testing
Bubble management Non-PGM catalysts
Membranes
Synopsis of Photoelectrode-based Approaches
Approach 1: Stabilize
High Efficiency Systems
Approach 2: Enhance Efficiency in Thin-Film Materials
Effic
ienc
y
Durability
DOE Targets: >1000h @STH 10-25%
Projected PEC Cost: $2 - 4/kg H2
Approach 3: Develop
3rd Generation Materials and
Structures
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Approach – HydroGEN EMN
https://www.h2awsm.org/capabilities
DOE EMN
HydroGEN Core labs capability
nodes
Data Hub
FOA ProposalProcess
• Proposal calls out capabilitynodes
• Awarded projects get access to nodes
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Approach – EMN HydroGEN
• Cost • Efficiency • Durability
PEC: Photoelectrochemical Electrolysis Barriers
PEC Node Labs PEC Projects Support through:
Personnel Equipment Expertise Capability Materials
Data
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Collaboration: 56 PEC Nodes, 2 Supernodes
Analysis: 2 Characterization: 15 Computation: 8 Synthesis: 5
Analysis: 2 Characterization: 13 Computation: 6 Synthesis: 5
Analysis: 3 Characterization: 3 Computation: 3 Synthesis: 2
Category Readiness
Level 1
Category Readiness
Level 2
Category Readiness
Level 3
• Nodes comprise equipment and expertise including uniqueness
• Category refers to availability and readiness • Many nodes span classification areas
16 (13 by FOA) Nodes utilized 18 Lab PIs engaged
100s of files on Data Hub
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Collaboration: HydroGEN PEC Node Utilization
Lab Node Hawaii Stanford Rutgers Michigan Super
LLNL Material Design and Diagnostics
✓ ✓
LLNL Interface Modeling ✓ ✓ ✓
LBNL Multiscale Modeling ✓
NREL Structure Modeling ✓
NREL MOVPE ✓ ✓ ✓
NREL CIGS ✓
NREL Combi/High Throughput ✓ ✓
NREL Surface Modifications ✓
Computation Material Synthesis
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LBNL Corrosion LBNL/ NREL
RDE/Cell Testing
LBNL Prototyping LBNL Photophysical Characterization
NREL Surface Analysis Cluster Tool
NREL PEC Characterizations LBNL On-Sun Testing
NREL On-Sun Efficiency Benchmarking
NREL Corrosion Analysis of Materials
LBNL In situ APXPS and XAS
Collaboration: HydroGEN PEC Node Utilization
Lab Node Hawaii
Characterization
Stanford Rutgers Michigan Super DMREF ✓ ✓
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• 5x funded LTEProjects
• Drawing from ??nodes
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Protective Catalyst Systems on III-V and Si-based Semiconductors for Efficient, Durable Photoelectrochemical Water Splitting Devices
Stanford University #P161
Accomplishments in BP1 Focus of BP2
Goals: • To develop unassisted water splitting devices that can
achieve > 20% solar-to-hydrogen (STH) efficiency. • Devices that can operate on-sun for at least 2 weeks. • Devices tat can provide a path toward electrodes that
cost $200/m2 by incorporating earth-abundant protective catalysts and novel epitaxial growth schemes.
https://h2awsm.org/capabilities/sun-photoelectrochemical-solar-hydrogen-
benchmarking
Fabrication Approach towards DOE Targets
On-sun Testing In Situ Spectroscopy
Go/No-Go #1: Photoelectrode that achieves >10mA/cm2 under 1 sun for >100h
Go/No-Go #2: Unassisted PEC water-splitting with non-precious metal HER catalyst that achieves STH >5% under 1 sun
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HydroGEN: Advanced Water Splitting Materials
Best-in-class Platinum Group Metal-free Catalyst Integrated Tandem Junction PEC Water Splitting Devices
Rutgers University #P160 Goals: High-Performance (HP) devices High-Value (HV) devices
Goal: >10% STH, > 100h durability Goal: ~10% STH, > 100h durability
Electrolyte 4H+ O2 Light
p i n p-n+ 2H22H2O
Ni5P4 LiCoO2 LiCoO2 TF catalyst Ni5P4 TF-eCAT TF-eCAT Silicon TF Protection layer HER OER TF Protection layer GaInP2/GaAs TCO
TiN thin film (TF) protection layer Tandem devices Perovskites (Inorganic-organics or oxynitrides)
Accomplishments in BP1 Focus of BP2 Successful TF integration STH = 11.5% HP devices
of Ni5P4/TiN on GaInP > 120 h duration (half-cell) • STH >12% by 2nd GEN upright tandem + 2-electrodes configuration
window layer • Extend the tandem device stability > 2days
Ni5P4/TiN on tandem Glass HV devices TCO
Ni0.52P0.34O0.17 • Demonstrate half-cell Perovskites Ti0.39N0.17O0.39P0.03 performance with Metal contact
Ga0.30In0.18P0.51 0.5 M H2SO4
perovskites absorbers & Si eCATS.
Protection layer Ni5P4 Catalyst
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Strengthen theory, synthesis and advanced characterization “feedback loop” to accelerate the development of efficient materials for H2 production.
Project Vision
Develop innovative technologies to synthesize and integrate chalcopyrites into efficient and low-cost PEC devices.
Project Goal
N. Gaillard (Device integration)
Addressing materials efficiency, durability & integration barriers through multi-disciplinary research.
C. Heske (Spectroscopy)
T. Jaramillo (Catalysis/Corrosion)
T. Ogitsu (Theory)
J. Cooper (Carrier dynamics)
K. Zu (absorbers) A. Zakutayev (junctions)
T. Deutsch (benchmarking)
Printable CuInSe2 with high conversion efficiency
PRINT & HEAT
1) Materials efficiency/cost barriers
Photoconversion efficiency > 70%
of theoretical max (GNG #1/2)
WO3 ALD coatings (3 nm) on 1.8 eV CuGa3Se5
2) Materials durability barrier
J>5 mA/cm2 for over 500 hrs of continuous operation (GNG #2/2)
Expend printable CuInSe2 baseline process to novel wide bandgap chalcopyrites
1) Materials efficiency/cost barriers Demonstrate chalcopyrite-based tandem device integration with exfoliation/transfer techniques
2) Materials integration barrier
e.g. Cu(In,B)Se2 with 40-60% B content
Theoretical prediction of Cu(In,B)Se2 bandgap as a function of boron content
Cu(In,Al)Se2 with 20-40% Al content
Exfoliation Transfer/Bonding
Accomplishments in BP1 Focus of BP2
Ag n.w.
Novel Chalcopyrites for AdvancedPhotoelectrochemical Water-Splitting
University of Hawaii #P162
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HydroGEN: Advanced Water Splitting Materials
Monolithically Integrated Thin-Film/Si TandemPhotoelectrodes
University of Michigan #P163 Goal: Develop Si-based low cost tandem photoelectrodes to achieve high efficiency (>15%) and stable (>1,000 hrs) water splitting systems
Approach: (i) The use of Si and GaN, the two most produced semiconductors, for scalable, low cost manufacturing; (ii) The incorporation of nanowire tunnel junction for high efficiency operation; (iii) The discovery of N-rich GaN surfaces to protect against photocorrosion and oxidation
Accomplishments in BP1
First demonstration of functional Si/InGaN tandem photoelectrode
Focus of BP2 Design, modeling, epitaxy/ synthesis, testing, and spectroscopic and kinetic studies of InGaN/Si double-junction photoelectrodes:
Achieve Si-based low cost PEC water splitting device with STH >10%
Achieve stable operation >500 hrs by using N-rich GaN self-protection
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OER Supernode: Approach (utilize 6 nodes)
Goal: Validated multiscale modeling to understand OER across pH scale using a modeling framework on IrO2 informed and validated by experiments
Catalyst surface
Ea and ∆Grxn for each elementary
step
DFT calculations
Continuum transport
Microkinetic model
Species flux at catalyst surface
Species activity near the catalyst
Concentration profiles
structure
Surface intermediate
coverage
RDE
AP XPS
Microelectrode
OER rates and
mechanism
Species activity near the catalyst
MD/DFT simulations
Double-layer structure
Species concentration near double layer
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OER Supernode: Results
Acid mechanism Alkaline mechanism
OH- + *OOH ↔ * + O2 + H2O + e-
Co-adsorption Pathway (calculating): O* + OH* → O* + O* + H* → O2 * + H* → O2 +
H*
H2O + * ↔ *OH + H+ + e-
*OH ↔ *O + H+ + e-
H2O + *O ↔ *OOH + H+ + e-
*OOH ↔ * + O2 + H+ + e-
OH- + * ↔ *OH + e-
OH- + *OH ↔ *O + H2O + e-
OH- + *O ↔ *OOH + e-
Accomplishments: •Developed methodology and intersections between the mathematical models
•Transfer of surface states and topology in vacuum to solvent simulation •Transfer of energy barriers to microkinetics •Microkinetics incorporated into continuum transport simulations
•Established ab-initio computational spectroscopy methods and experiments to validate theoretical structural models •Initial measurements of kinetic rates and surface species on IrO2 HydroGEN: Advanced Water Splitting Materials
HydroGEN: Advanced Water Splitting Materials
OER Supernode: Future Work
• Experiments on IrO2 – Measure OER kinetics in alkaline, acid, and neutral (buffer) solutions using RDE – Measure OER kinetics with alkaline and acid ionomers in microelectrode setup – Measure and quantify surface species using ambient-pressure XPS and
concomitant modeling
• Calculations – Calculate free-energy barriers and reaction mechanisms as a function of
• Applied potential • Electrolyte composition • Species concentration • Surface coverage
– Estimate the effect of pH variation and/or bias potential on the OER reaction pathways
– Examine possibility of site-exchange for OER on IrO2
• Incorporate the knowledge gained in the multiscale modeling framework and compare to experimental data
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PEC Supernode Approach
Goal: Understand integration issues and emergent degradation mechanisms of PEC devices at relevant scale, and demonstrate an integrated and durable 50 cm2 PEC panel.
LBNL
NREL
PEC Cell Scale up
Commercial PVs
1cm2 4cm2 8cm2
PV Cell Scale up 0.1cm2 1 cm2 4 cm2 8 cm2
Benchmarking In situ degradation and characterization Emerging Degradation Pathways Modeling
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PEC Supernode: Results
Scale up of LBNL PEC Devices Scale up of NREL PV/PEC Cells 0.1 cm2 PV
Accomplishments: •Benchmarking PV and PEC cell performance between Labs •PV fabrication scale up from 0.1 to 1cm2
•PEC vapor cell scale up from 1 to 4 cm2
1 cm2 PEC
4 cm2 PEC
1 cm2 PV Anode Flowfield/GDL
PEM
Cathode Flowfield/GDL
Benchmarking PV/PEC Performance LBNL 1cm2 PEC
Vapor Cell with commercial PV NREL 1cm2 PV
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PEC Supernode: Future Work
PV scale up • Developing GaInP/GaAs growths on a
newer 2” reactor • GaInP quality not quite as good
yet, but we are making progress • In the process of testing the uniformity
of the IV curves for tandems over a 2” wafer
• Upcoming plans to make processing masks for 4 cm2 and 8 cm2 devices
• Characterize freshly prepared PVs and after PEC testing
PEC scale up • Continue scale up and
evaluation of 4 cm2 vapor and liquid PEC cells
• Translate to 8 cm2 PEC cells • Benchmark performance
and durability with NREL • On sun and diurnal testing
Degradation and Modeling • Integrate in situ durability testing via
ICPMS • Visualization of gas and liquid water
bubble formation in vapor/liquid cells and feed modeling effort
• Model emergent degradation mechanisms and define cell geometries
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HydroGEN: Advanced Water Splitting Materials
Engagement with 2B Team
• Collaboration with 2B Team Benchmarking Project
• All HydroGEN PEC node capabilities were assessed for AWS technology relevance and readiness level
• PEC data metadata definitions exchanged
• PEC questionnaire responses collated and disseminated – Defining: baseline materials sets, test cells, testing conditions – Published on the DataHub
• 2B working groups and annual meeting
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HydroGEN: Advanced Water Splitting Materials
Future Work
• Leverage HydroGEN Nodes at the labs to enable successful budget period 2 activities – Increased durability and lifetime – Decrease cost
• Conduct case studies and integrated research in 2 supernodes – PEC scaleup and integration – OER multiscale modeling
• Enable and work with possible new seedling projects • Work with the 2B team and PEC working group to further
establish testing protocols and benchmarks • Utilize data hub for increased communication, collaboration,
generalized learnings, and making digital data public • Leverage community resources
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HydroGEN: Advanced Water Splitting Materials
Summary
• Supporting 4 FOA projects with 13 nodes and 11 PIs – Synthesis, benchmarking, modeling, characterization – 100s of files on the data hub and numerous exchanged samples – Personnel exchange of postdocs, students, and PIs to the labs
• Working closely with the project participants to advance knowledge and utilize capabilities and the data hub
• Projects demonstrate improvements in durable, less expensive materials with high performance and improved durability
• Future work will include continuing to enable the projects technical progress and develop & utilize lab core capabilities
• Supernode research underway to integrate nodes and systematic exploration of critical PEC-related questions
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Acknowledgements
Authors
PEC Project Leads
Eric Garfunkel Tom Jaramillo Nicolas Gaillard Zetian Mi
Adam Weber Todd Deutsch Nemanja Danilovic Huyen Dinh
Research Teams
Acknowledgements
PEC Supernode Team
Todd Deutsch James Young Myles Steiner Dan Friedman
Adam Weber Frances Houle Nemanja Danilovic Francesca Toma Tobias Kistler Guosong Zeng
Best Practices in Materials Characterization PI: Kathy Ayers, Proton OnSite (LTE)Co-PIs: Ellen B. Stechel, ASU (STCH);
Olga Marina, PNNL (HTE);CX Xiang, Caltech (PEC)
Lien-Chung Weng David Larson Jefferey Beeman
Acknowledgements
OER Supernode Team
Adam Weber Ethan Crumlin Nemanja Danilovic David Prendergast Lien-Chung Weng
Tadashi Ogitsu Brandon Wood Tuan Anh Pham
Ross Larsen Mai-Anh Ha Shaun Alia